CAREER: Theoretical Analysis of Molecular Oxygen Chemistry in Biological Systems

威斯康星大学的Qiang Cui通过CAREER奖获得理论与计算化学项目的支持，开发和应用混合量子力学/分子力学方法来探索黄素蛋白中黄素-氧化学的细节。具体来说，将使用约束密度泛函理论来构建与黄素和分子氧之间电子转移相关的绝热态。综合-平均密度泛函数理论将用于平衡描述黄素-超氧化物自由基对经历自旋禁止跃迁的三重态和单重态电子态。这些方法可以推广到与其他涉及分子氧的化学过程相关的能量学和动力学性质。此外，将为计算生物物理学课程开发完全互动的多媒体材料，以及具有重大教学价值的经典研究论文的网络数据库。理论分析在确定蛋白质活性位点环境的详细机制和提供结构和动力学特性的见解方面非常有价值，特别是在单独实验不确定的情况下。这个研究项目将扩大酶模拟的范围和细节水平，超越传统的计算方法所提供的。此外，新的多媒体教材和基于网络的数据库将通过结合现代发展和基本概念的平衡来改善学生的学习经验。

Qiang Cui of the University of Wisconsin is supported by the Theoretical and Computational Chemistry Program through a CAREER award to develop and apply hybrid quantum mechanical/molecular mechanical methods to explore details of flavin-oxygen chemistry in flavoproteins. Specifically, a constrained density functional theory will be used to construct diabatic states relevant to electron transfer between flavin and molecular oxygen. Ensemble-averaged density functional theory will be used to achieve a balanced description of both triplet and singlet electronic states of the flavin-superoxide radical pair undergoing a spin-forbidden transition. These methods can be extended to the energetics and kinetic properties associated with other chemical processes involving molecular oxygen. In addition, fully interactive, multimedia material will be developed for computational biophysics courses, along with a web-based database of classic research papers with great pedagogical value.Theoretical analysis is very valuable in identifying detailed mechanisms and providing insights into the structural and dynamical properites of protein active site environments, especially when experiments alone are inconclusive. This research project will expand the scope and level of detail for enzyme simulations beyond what conventional computational methods offer. In addition, new multimedia course material and a web-based database will improve the student learning experience by incorporating a balance of modern developments and fundamental concepts.